Acenes, such as aza-acenes are attractive materials for organic semiconductors, specifically for n-type materials. There are disclosed new derivatives of acenes that are fabricated using novel synthesis. For example, the disclosed fabrication strategies have allowed for the first time new aza-tetracene and aza-pentacene derivatives. The HOMO and LUMO energy levels of these materials are tunable through appropriate substitution and as predicted, deepened. There are also disclosed organic photosensitive devices comprising at least one aza-acene such as aza-tetracene and aza-pentacene.